TW200902685A - Phosphors consisting of doped garnets for pcLEDs - Google Patents
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Abstract
Description
200902685 九、發明說明： 【發明所屬之技術領域】 本發明係關於由Th4+、Sb3+、Ir3 +及/或Bi3 +共摻雜之石斤 石組成的磷光體、其製備及其作為LED轉換磷光體用於白 光LED或所謂的按需取色應用之用途。 【先前技術】 按需取色概念意謂藉助於使用一或多種磷光體之 pcLED(=磷光體轉換lED)產生特定色點之光。使用此概念 (^ 以（例如）產生某些公司設計，例如發光式公司標總、商標 等。 不 具有石榴石結構之習知磷光體（諸如純YAG:Ce或其衍生 物）在尤其高功率LED中使用時並不呈現最佳的光譜學性 質。此論述之理由如下： •磷光體表面使大部分初輻射散射，意謂磷光體無法吸 收此部分； , ·離子（尤其活化劑離子）在磷光體顆粒中之不均勻分布 U 導致内部量子產率減小； 300 nm之小單晶尺寸導致表面效應起主導作用··一方 面表面上存在之瑕疵引起晶格中之無輻射復合，而 另方面，罪近表面的活化劑離子存在於晶格之非均 曰曰％中且無法用於轉換效應或防止後者經由能量遷 移到達表面，此又與無輕射復合相關。200902685 IX. Description of the Invention: [Technical Field] The present invention relates to a phosphor composed of Th5+, Sb3+, Ir3+ and/or Bi3+ co-doped sarcophagus, preparation thereof and as LED conversion phosphor Used for white LEDs or so-called on-demand color picking applications. [Prior Art] The on-demand color picking concept means that light of a specific color point is generated by means of a pcLED (=phosphor conversion lED) using one or more phosphors. Use this concept (^ to, for example, produce certain corporate designs, such as illuminating corporate standards, trademarks, etc. Conventional phosphors without garnet structure (such as pure YAG: Ce or its derivatives) are particularly high power The best spectroscopy properties are not used in LEDs. The reasons for this discussion are as follows: • The phosphor surface scatters most of the primary radiation, meaning that the phosphor cannot absorb this part; • The ions (especially activator ions) are The uneven distribution of U in the phosphor particles leads to a decrease in the internal quantum yield; the small single crystal size of 300 nm causes the surface effect to dominate. · On the one hand, the presence of defects on the surface causes the non-radiative recombination in the crystal lattice, while In contrast, activator ions near the surface of the sin are present in the non-uniform % of the crystal lattice and cannot be used for conversion effects or to prevent the latter from reaching the surface via energy transfer, which in turn is associated with no light-lighting recombination.
• 磷光體中所產生之慈伞+ + A 费先之特疋部分無法離開磷光體， 因為其在與光疏環境之界面處全反射且經由波傳導過 129154.doc 200902685 程在填光體内遷移且最後經由再吸收而失去； • 進入鱗光體内的大部分初輻射無法被吸收，因為磷光 體因其激發態之長壽命（衰變時間Tl/e YAG:Ce=63_67 ns，視 Ce3+濃度而定’參見Weber M.J.，Solid State commun. (1973) 12，741)而飽和。 ΕΡ-0 142 931揭示一種視覺顯示器設備，其中使用具有 石榴石結構之磷光體，且基板材料大體上具有Υ3Α15〇ι2組 成。• The parasitic + + A pre-existing part of the phosphor cannot leave the phosphor because it is totally reflected at the interface with the light-diffusing environment and is transmitted through the wave. 129154.doc 200902685 Migration and finally lost through reabsorption; • Most of the primary radiation entering the scale is not absorbed because of the long lifetime of the phosphor due to its excited state (decay time Tl/e YAG: Ce = 63_67 ns, depending on Ce3+ concentration) And see 'Weber MJ, Solid State commun. (1973) 12, 741) and saturated. ΕΡ-0 142 931 discloses a visual display device in which a phosphor having a garnet structure is used, and the substrate material is substantially composed of Υ3Α15〇ι2.
EP-1095 998揭示一種具有A3B5〇12:(Ce，Pr)組成之磷光 體，其中A為來自Y、Tb、La及/或Lu之群的稀土金屬，且 B表不A1及/或Ga。 WO 2005/061659描述一種具有 A3B5〇i2(Ce，Pr，Eu)型之 石榴石結構的磷光體，其中A=稀土金屬且B=A1、Ga，其 中組分B中之一些已經Si置換。 目前用於含有發藍光晶片作為初輻射之白的磷 光體主要為YAG:Ce3+或其衍生物，或亦為經Eu2+摻雜的正 ，酸鹽（ca，sr，Ba)2si〇4。如下藉由固態擴散方法（亦稱為 混口及k製）製備磷光體：將粉末形式之氧化性起始材料 混合。，研磨該混合物且接著將該混合物於供箱中、在高達 1700〕之溫度下、在視需要還原性氣氛下煅燒長達數天。 此舉传到關於形態、粒徑分布及發光活化劑離子在基質體 積中之分布具有不均—性之碟光體粉末。此外，藉由傳統 方法所製備之該等磷光體的形態、粒徑分布及其他性質僅 可不良地調節且難以重現。因此，該等顆粒具有多種缺 129154.doc 200902685 點，詳言之，諸如由該等具有非最佳及非均—形態及師 分布之磷光體對LED晶片形成非均一塗層，其因散射而導 致高損耗過程。由於以下事實，在該等LED之產生中出現 其他損耗：LED晶片之磷光體塗層不僅不均一，且無法由 LED再生為LED。此導致由pcLED(甚至在一批次中）所發 射之光的色點發生變化。此使得lED之複雜揀選方法（所謂 的分級）成為必要。 【發明内容】 因此，本發明之目的係提供用於白光LED或用於按需取 色應用之轉換磷光體，其並不具有一或多個上文已提及之 缺點且產生暖白光。 驚人地，由於轉換磷光體由經鈽活化之Th3+、Sb3 +及/或 Bi3 +共摻雜石榴石組成（其中較佳摻雜劑以至少1〇〇沖爪之 濃度存在）而避免上文已提及之缺點，藉此可達成本發明 之目的。 另一驚人效果在於：與藉由固態擴散方法所製備之非共 摻雜YAG:Ce填光體相比，本發明之碟光體具有較高之發 光強度（比較圖1及2)。 因此，本發明係關於具有式I之石榴石結構之鱗光體： (Y^GdbXUcSed^meJbftPrgJhhJri^bpBiOs-xCA^Ga^sOn^ex 其中： a+b+c+d+e+f+g+h+i+j+k= 1 5 l+m=l，且 129154.doc 200902685 x=0,005 至 〇. 1。 本文中之石權石結構亦自然地意謂基於與石權石之理想 情形稍微不同之瑕庇或晶格缺陷的結構，只要此晶體保持 典型石權石結構。典型石權石結構通常意謂A3B5〇12:D ’ 其中A稀土金屬（RE) ; B=A1、Ga ;且〇=置換RE之活化 劑，諸如鈽。 鈽之摻雜濃度較佳介於〇5與1〇重量％之間。尤其較佳介 於2.0與5.G重量％之間，且最佳介於3.0與3.5重量％之間。 在介於3.0與3.5%之間的飾濃度下，通常出現增加之吸收 及因此增加之光產率或較大之鱗光體亮度。較高之飾濃度 會使量子產率降低且從而又使光產率降低。 式I之發光材料之吸收及發射光譜、熱淬火行為及衰變 時間Tl/e高度取決於三價陽離子之精確組成。上文已提及 光谱性質之關鍵因辛為f + 一 J规U京為Ce之十一面體方位的晶場強度或 ίEP-1095 998 discloses a phosphor having the composition A3B5〇12:(Ce,Pr), wherein A is a rare earth metal from the group of Y, Tb, La and/or Lu, and B represents A1 and/or Ga. WO 2005/061659 describes a phosphor having a garnet structure of the A3B5〇i2(Ce, Pr, Eu) type, wherein A = rare earth metal and B = A1, Ga, wherein some of the components B have been replaced by Si. The phosphor currently used for white containing a blue-emitting wafer as the initial radiation is mainly YAG:Ce3+ or a derivative thereof, or is also an Eu2+-doped ortho-acid salt (ca,sr,Ba)2si〇4. Phosphors are prepared by solid state diffusion methods (also known as mixing and k-making) by mixing oxidative starting materials in powder form. The mixture is ground and then the mixture is calcined in a tank at a temperature of up to 1700 Å for up to several days under an optional reducing atmosphere. This is carried out to a disc powder having an unevenness in morphology, particle size distribution, and distribution of luminescent activator ions in the matrix volume. Moreover, the morphology, particle size distribution and other properties of the phosphors prepared by conventional methods can only be poorly adjusted and difficult to reproduce. Thus, the particles have a variety of defects 129,154.doc 200902685, in particular, such as by the non-optimal and non-uniform-form and teacher-distributed phosphors forming a non-uniform coating on the LED wafer due to scattering Lead to high loss processes. Other losses occur in the generation of such LEDs due to the fact that the phosphor coating of the LED wafer is not only non-uniform and cannot be regenerated by the LED into an LED. This causes the color point of the light emitted by the pcLED (even in a batch) to change. This necessitates a complex picking method (so-called grading) of lED. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a conversion phosphor for white LEDs or for on-demand color picking applications that does not have one or more of the disadvantages mentioned above and that produces warm white light. Surprisingly, since the conversion phosphor consists of yttrium-activated Th3+, Sb3+ and/or Bi3+ co-doped garnets (where the preferred dopant is present in at least one 〇〇 claw concentration) The disadvantages mentioned are thus attained for the purpose of the invention. Another surprising effect is that the disc of the present invention has a higher light intensity than the non-co-doped YAG:Ce fill prepared by the solid state diffusion method (compare Figures 1 and 2). Accordingly, the present invention relates to a squama having a garnet structure of the formula I: (Y^GdbXUcSed^meJbftPrgJhhJri^bpBiOs-xCA^Ga^sOn^ex where: a+b+c+d+e+f+g+ h+i+j+k= 1 5 l+m=l, and 129154.doc 200902685 x=0,005 to 〇. 1. The stone weight structure in this paper also naturally means that it is based on the ideal situation with Shiquanshi A structure with different barriers or lattice defects, as long as the crystal maintains a typical stone weight structure. A typical stone weight structure usually means A3B5〇12:D 'where A rare earth metal (RE); B=A1, Ga; 〇 = an activator for replacing RE, such as ruthenium. The doping concentration of ruthenium is preferably between 〇5 and 1% by weight, particularly preferably between 2.0 and 5.g% by weight, and optimally between 3.0 and Between 3.5% and 5%. At a decorative concentration between 3.0 and 3.5%, there is usually an increase in absorption and thus an increase in light yield or a larger scale brightness. Higher decoration concentrations will result in quantum production. The rate is reduced and thus the light yield is reduced. The absorption and emission spectra, the thermal quenching behavior and the decay time Tl/e of the luminescent material of the formula I are highly dependent on the precise composition of the trivalent cation. As mentioned above, the key reason for the spectral properties is the crystal field strength of the eleven plane of the Ce.
Ce-Ο鍵之共價特性，亦即氧陰離子之有效負電荷及陰離子 與金屬軌道之重疊。 一般而t ’可觀測到隨著晶場強度增加或共價特性增 強，Ce3 +發射帶（[Xe]5dl — [Xe]4f】躍遷）偏移至紅光光言; 區内。因此’上式1之組合物或經富電子(”可易於氧化”)： 價陽離子摻雜之組合物產生沿此方向受影響的光譜性質了 尤其青睞式I之璘光體，其中式！化合物為選自式^至式 IV化合物之化合物·· > (Π)； 129154.doc 200902685 (Y^-yCexBiyhAlsOu，其中 0.005 S χ 幺 0.1 且0.001 幺 y 幺 0.005 (III); (Yi-x_yCexThx)3Al5012，其中 0_005 < x S 0.1 且0·001 < y < 0.005 (IV)。 石榴石結構中之一或多種組分Bi、Sb或Th之比例的增加 使本發明磷光體之發射波長向紅光偏移。此對於產生暖白 光尤為重要。為產生具有高顏色重現性之舒適光，最好使 用不同磷光體之混合物，即綠光偏移磷光體（諸如 YdAl’GahC^2)與本發明磷光體及紅光磷光體（例如，可提 供局流明當量之紅光帶或紅光譜線發射極，諸如推雜銪之 鎢酸鹽、鉬酸鹽及/或磷酸鹽）之混合物。此外，亦可將藍 光-綠光磷光體混雜，諸如Lu3Al5012:Ce(LUAG:Ce)。此產 生與太陽之VIS日光光譜極其類似之近似連續發射光譜。 本發明碟光體之粒徑介於50 nm與3 0 μιη之間，較佳介於 1 μηι與 20 μηι之間。 在另一實施例中，式I之構光體可另外包含以下碟光體 材料中之至少一種其他材料：具有一或多種活化劑離子 (諸如Ce、Eu、Mn、Cr及/或Bi)之各單獨氧化物、鉬酸 鹽、鎢酸鹽、釩酸鹽、III族氮化物、（氧基）氮化物，或其 混合物。 若欲建立特定色空間，則此尤為有利。 在另一較佳實施例中，磷光體在LED晶片之對面具有結 構化（例如錐狀）表面（參見DE 1〇2〇〇6〇5433〇 〇, Merck，其 以全文引用方式併入本申請案之上下文中）。此致能儘可 能多的光耦離磷光體。 129154.doc 10 200902685 磷光體上之結構化表面係藉由冑後用已經結構化之適當 材料土覆而產生’或在後續步驟中藉由(光)微影方法、蝕 刻方法或藉由使用能束或材料束或機械力作用之寫入方法 而產生。The covalent property of the Ce-Ο bond, that is, the effective negative charge of the oxyanion and the overlap of the anion with the metal orbital. In general, t ′ can be observed as the intensity of the crystal field increases or the covalent property increases, and the Ce3 + emission band ([Xe]5dl — [Xe]4f] transition) shifts to the red light; Thus, the composition of Formula 1 above or rich in electrons ("Easy to oxidize"): The valence cation doped composition produces spectral properties that are affected in this direction. Especially favoring the phosphor of Formula I, where! The compound is a compound selected from the group consisting of the compound of the formula IV to the compound of the formula IV. (Π); 129154.doc 200902685 (Y^-yCexBiyhAlsOu, wherein 0.005 S χ 幺 0.1 and 0.001 幺y 幺 0.005 (III); (Yi-x_yCexThx 3Al5012, where 0_005 < x S 0.1 and 0·001 < y < 0.005 (IV). An increase in the ratio of one or more components Bi, Sb or Th in the garnet structure causes the emission of the phosphor of the invention The wavelength shifts toward red light. This is especially important for producing warm white light. To produce comfortable light with high color reproducibility, it is best to use a mixture of different phosphors, ie green offset phosphors (such as YdAl'GahC^2). And phosphors of the present invention and red phosphors (for example, red light bands or red spectral line emitters, such as tweezers of tungstate, molybdate and/or phosphate, which provide a lumen equivalent) In addition, a blue-green phosphor may also be intermixed, such as Lu3Al5012:Ce(LUAG:Ce), which produces an approximately continuous emission spectrum that is very similar to the solar VIS solar spectrum. Between 50 nm and 30 μm, preferably between 1 μηι and 20 μη In another embodiment, the illuminator of Formula I may additionally comprise at least one other material of the following disc materials: having one or more activator ions (such as Ce, Eu, Mn, Cr, and/or Each of the individual oxides, molybdates, tungstates, vanadates, group III nitrides, (oxy)nitrides of Bi), or mixtures thereof. This is particularly advantageous if a particular color space is to be created. In a preferred embodiment, the phosphor has a structured (e.g., tapered) surface opposite the LED wafer (see DE 〇 〇〇 〇 〇 〇 〇〇 〇〇 Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer Mer In this context, it is possible to couple as much optocoupler as possible from the phosphor. 129154.doc 10 200902685 The structured surface on the phosphor is produced by rubbing it with a suitable material that has been structured and then in the next step. It is produced by a (photo) lithography method, an etching method, or by a writing method using a beam or a material beam or a mechanical force.
在另較佳實施例中’本發明之磷光體在led晶片之對 面具有粗糙表面，該粗糙表面攜有Si〇2、Ti〇2、八丨2〇3、 Zn〇2、Zr〇2及/或Ah之奈米顆粒或該等材料之組合或包 含鱗光體組合物之顆粒之組合。本文中之祕表面具有高 達數百奈米之粗縫度。經塗覆表面之優點在於可減少或防 止王反射且可使光較佳地耦離本發明之磷光體（參見DE 102006054330.〇(Merck) 之上下文中）。 其以全文引用方式併入本申請案 此外，本發明之磷《體較佳在朝向遠離晶片之方向的表 面具有折射率經調適之層，其簡化初㈣及/或磷光體元 件所發射之輻射的耦離。 在另一較佳實施例中，磷光體具有由si〇2、丁丨〇2、 Al2〇3、ZnO、Zr〇2及/或Υ2〇3或其混合氧化物組成之連續 表面塗層。此表面塗層之優點在於可經由塗層材料折射率 之適當分度來實現折射率對環境之適應。在此情況下，磷 光體表面上光之散射減》1較大比例之光可穿透至填光體 中且於其中經吸收且轉換。此外，折射率經調適之表面塗 層因全内反射減少而致能較多之光耦離磷光體。 此外’若携光體必須經封裝，則連續層為有利的。此可 為必需的，以抵消磷光體或其部分對徑直鄰近之擴散水或 129154.doc 200902685 其他材料之敏感性。用連續外鞘封裝之另一原因為實際磷 光體因晶片中所形成之熱而熱解耗。此熱導致鱗光體之榮 光產率減小且亦可影響Μ顏色。最終，此類型之塗層藉 由防止形成於鱗光體中之晶格振動傳播至環境内而致能鱗 光體之效率增加。 此外，磷光體較佳具有由Si〇2、Ti〇2、Al2〇3、Ζη〇、 〇2及/或Υ2〇3或其此合氧化物組成或由磷光體組合物組In another preferred embodiment, the phosphor of the present invention has a rough surface opposite the LED wafer, the rough surface carrying Si〇2, Ti〇2, barium 2〇3, Zn〇2, Zr〇2 and/or Or a combination of Ah nanoparticles or a combination of such materials or particles comprising a scale composition. The secret surface in this paper has a rough seam of up to several hundred nanometers. The coated surface has the advantage that the reflection of the king can be reduced or prevented and the light can be preferably coupled away from the phosphor of the invention (see DE 10 2006 054 330. M (Merck). It is incorporated herein by reference in its entirety. In addition, the phosphor of the present invention preferably has a refractive index-adapted layer on a surface facing away from the wafer, which simplifies the radiation emitted by the primary (four) and/or phosphor elements. Coupling. In another preferred embodiment, the phosphor has a continuous surface coating consisting of si 〇 2, butyl lanthanum 2, Al 2 〇 3, ZnO, Zr 〇 2 and/or Υ 2 〇 3 or a mixed oxide thereof. An advantage of this surface coating is that the refractive index can be adapted to the environment via an appropriate indexing of the refractive index of the coating material. In this case, a large proportion of the light scattering on the surface of the phosphor can be penetrated into the fill and absorbed therein and converted. In addition, the refractive index-adapted surface coating is more photocoupled from the phosphor due to reduced total internal reflection. Furthermore, a continuous layer is advantageous if the light-carrying body has to be encapsulated. This may be necessary to counteract the sensitivity of the phosphor or part thereof to the directly adjacent diffusion water or other materials. Another reason for packaging with a continuous outer sheath is that the actual phosphor is thermally depleted due to the heat formed in the wafer. This heat causes the brilliance of the scale to decrease and the color of the enamel can also be affected. Ultimately, this type of coating increases the efficiency of the luminosity by preventing the lattice vibrations formed in the scale from propagating into the environment. Further, the phosphor preferably has a composition consisting of Si〇2, Ti〇2, Al2〇3, Ζη〇, 〇2 and/or Υ2〇3 or a combination thereof or a composition of the phosphor composition
成之多孔表面塗層。該等多孔塗層為進—步降低單層之折 射率提供可能性。 此類型之多孔塗層可藉由如wo 03/027015(其以全文引 用方式併人本中請案之上下文中）中所述之三種習知方法 而產生.蝕刻玻璃（例如鹼石灰玻璃（參見us 4019884)); 塗佈多孔層；及多孔層與蝕刻方法之組合。 在另車乂佳實她例中，_光體具有搞有促進與環境化學 鍵結之官能基之表面’其較佳由環氧或聚錢樹脂組成。 該等官能基可為（例如）經由側氧基鍵結且能_基於環氧 化物及/或聚魏之黏結劑組分形成鍵聯的g旨或其他衍生 物。此類型表面之優點在於促進將磷光體均勾混合於黏結 d中此外’碟光體/黏結劑系統之流變學性質以及適用 期可因此在某種程度上經調節。因此，使混合物之處理簡 化。 由於塗佈於LED晶片μ + 士 & 出， 月上之本發明鱗光體層較佳由聚石夕氧 與均勻構光體顆粒之、、曰人^^ &上 此s物組成且聚矽氧具有表面張力， 因此該磷光體層在鞀與> _ 隹頌喊水準下不均一，或層厚度並非始終 129154.doc 12 200902685 恆定。 此外，本發明亦係關於可如下獲得之具有石榴石結構之 磷光體：藉由濕式化學方法及後續熱後處理將含鋁、含釔 及含鈽之起始材料與至少一種含銻、含鉍、含銥及/或含 銼之共摻雜劑及視需要其他含釓、含縳、含硒、含彭、含 錢、含镨及/或含鎵之材料混合。 如上所述’用於製備磷光體之起始材料由基質材料（例 如銘、紀及鈽之鹽溶液）及至少一種含Sb、含Bi、含Ir或含 ί Th之摻雜劑及視需要其他含Gd、含Lu、含Sc、含Sm、含A porous surface coating. These porous coatings offer the possibility of further reducing the refractive index of the single layer. Porous coatings of this type can be produced by three conventional methods as described in WO 03/027015, which is hereby incorporated by reference in its entirety in its entirety in the the the the the the the the the Us 4019884)); coating a porous layer; and combining a porous layer with an etching method. In another example, the glaze has a surface which promotes functional groups bonded to environmental chemistry. It is preferably composed of epoxy or polyphenol resin. The functional groups can be, for example, g- or other derivatives that are bonded via a pendant oxy group and that can form a bond based on the epoxide and/or poly-based binder component. An advantage of this type of surface is that it facilitates the incorporation of phosphors into the bond d. Furthermore, the rheological properties of the <span/body system and the pot life can be adjusted to some extent. Therefore, the treatment of the mixture is simplified. The squamous layer of the present invention, which is coated on the LED wafer, is preferably composed of polysulfide and uniform illuminating particles, and is composed of the sigma and the s The oxygen has a surface tension, so the phosphor layer is not uniform under the 鼗 and > _ shouting level, or the layer thickness is not always 129154.doc 12 200902685 constant. In addition, the present invention also relates to a phosphor having a garnet structure which can be obtained by a wet chemical method and a subsequent thermal post-treatment of a starting material containing aluminum, cerium and cerium, and at least one cerium-containing, Co-dopants containing antimony, antimony and/or antimony and, if desired, other materials containing antimony, bound, selenium, penton, money, antimony and/or gallium. As described above, the starting material for preparing the phosphor is composed of a matrix material (for example, a salt solution of Ming, Ji and Yu) and at least one dopant containing Sb, Bi, containing Ir or containing Th and other optionally Contains Gd, contains Lu, contains Sc, contains Sm, contains
Tb、含Pr及/或含Ga之材料組成。合適之起始材料為溶解 及/或懸浮於無機及/或有機液體中之無機及/或有機物質， 諸如金屬、半金屬、過渡金屬及/或稀土金屬之硝酸鹽、 碳酸鹽、碳酸氫鹽、填酸鹽、緩酸鹽、醇化物、乙酸鹽、 草酸鹽、齒化物、硫酸鹽、有機金屬化合物、氫氧化物及/ 或氧化物。較佳地使用含有具有必要化學計量比之對應元 素的經混合之硝酸鹽溶液、氣化物或氫氧化物溶液。 此外’本發明亦係關於一種用於製備磷光體之方法’其 具有以下方法步驟： a) 藉由濕式化學方法將至少三種選自含γ、含A1、含 Ce、含Gd、含Lu、含Sc、含Sm、含Tb、含Pr及/或 含Ga之材料的起始材料混合，藉此製備與來自磷光 體則驅物懸浮液或溶液之含Sb、含bi及/或含Th的材 料共摻雜之經鈽活化磷光體； b) 對Sb、Bi及/或Th共摻雜之磷光體進行熱後處理。 129154.doc -J3 - 200902685 濕式化學製備優於習知固態擴散方法之處一般在於製備 本發明磷光體顆粒時所得之材料的化學計量組成、粒徑及 形態具有較大均一性。 對於由（例如）硝酸記、硝酸鋁、硝酸鈽及硝酸鉍溶液之 混合物組成的磷光體之水性前驅物（磷光體前驅物）之濕式 化學預處理而言，以下已知方法為較佳的： •用NH4HC〇3溶液共沈澱（參見例如J5/仍— Lehrbuch der analyt. u. prap. anorg. Chem. [Textbook ( 〇f Analyt. and Prep. Inorg. Chem.] 2002) 〇 •使用样檬酸與乙二醇之溶液的pecchini方法（參見例如 Annual Review of Materials Research ^ : 2006, 28J-33J)。 •使用脲之燃燒方法。 •將水溶液或有機鹽溶液（起始材料）噴霧乾燥。 •將水溶液或有機鹽溶液（起始材料）噴霧熱解。 •蒸發硝酸鹽溶液且對殘餘物進行熱轉化。 在上文已提及之共沈澱法中，將（例如）NH4HC03溶液添 加至相應磷光體起始材料之硝酸鹽溶液中，從而形成磷光 - 體前驅物。 在Pecchini方法中，在室溫下將（例如）由檸檬酸與乙二 醇組成之沈澱試劑添加至相應磷光體起始材料之上文已提 及肖S文/谷液中，且隨後加熱混合物。增加黏度會引起填 光體前驅物形成。 在已知燃燒方法中，將相應磷光體起始材料之上文已提 129154.doc •14· 200902685 及硝酸鹽溶液（例如）溶解於水 , 接者在回流下沸騰且用 处里攸而引起磷光體前驅物之緩慢形成。 喷霧熱解法為氣溶膠方法之—， 其特徵為將溶液、懸浮 液或刀散液噴霧至以多種方式 肉η π 式加熱之反應空間（反應器） 且固體顆粒形成且沈積。與使用 <戰之熱氣溫度的 喷霧乾燥相比，在作為g、,w ...... 為回Μ方法之噴霧熱解法中，除溶劑 另外發生所用起始材料（例如鹽）之熱分解及物 (例如乳化物、混合氧化物)之再形成。Composition of Tb, Pr-containing and/or Ga-containing materials. Suitable starting materials are inorganic and/or organic substances which are dissolved and/or suspended in inorganic and/or organic liquids, such as nitrates, carbonates, hydrogencarbonates of metals, semimetals, transition metals and/or rare earth metals. , acid salt, buffer acid salt, alcoholate, acetate, oxalate, tooth, sulfate, organometallic compound, hydroxide and/or oxide. Preferably, a mixed nitrate solution, vapor or hydroxide solution containing corresponding elements having the requisite stoichiometric ratio is used. Furthermore, the invention also relates to a method for preparing a phosphor which has the following method steps: a) at least three selected from the group consisting of gamma containing, containing A1, containing Ce, containing Gd, containing Lu, by wet chemical methods. Mixing materials containing Sc, Sm-containing, Tb-containing, Pr-containing, and/or Ga-containing materials, thereby preparing Sb-containing, bi-containing, and/or Th-containing materials from a phosphorous suspension or solution The material is co-doped with a ruthenium-activated phosphor; b) the Sb, Bi and/or Th co-doped phosphor is thermally post-treated. 129154.doc -J3 - 200902685 The wet chemical preparation is superior to the conventional solid state diffusion method in that the stoichiometric composition, particle size and morphology of the material obtained when preparing the phosphor particles of the present invention are largely uniform. For wet chemical pretreatment of an aqueous precursor (phosphor precursor) of a phosphor consisting of, for example, a mixture of nitric acid, aluminum nitrate, cerium nitrate and cerium nitrate solution, the following known methods are preferred. : • Coprecipitation with NH4HC〇3 solution (see for example J5/still – Lehrbuch der analyt. u. prap. anorg. Chem. [Textbook ( 〇f Analyt. and Prep. Inorg. Chem.] 2002) 〇 • Use of lemon A pecchini method of a solution of an acid and an ethylene glycol (see, for example, Annual Review of Materials Research ^ 2006, 28J-33J). • A combustion method using urea. • Spray drying an aqueous solution or an organic salt solution (starting material). The aqueous solution or organic salt solution (starting material) is spray pyrolyzed. • The nitrate solution is evaporated and the residue is thermally converted. In the coprecipitation method already mentioned above, for example, a NH4HC03 solution is added to the corresponding phosphorescence. a phosphorescent precursor in the body starting material to form a phosphorescent precursor. In the Pecchini method, a precipitation reagent consisting, for example, of citric acid and ethylene glycol is added to the corresponding solution at room temperature. The light body starting material has been mentioned above in the Schiffon/Valley solution, and then the mixture is heated. Increasing the viscosity causes the formation of the filler precursor. In the known combustion method, the corresponding phosphor starting material is The above mentioned 129154.doc •14· 200902685 and the nitrate solution (for example) are dissolved in water, and the carrier is boiled under reflux and used in the sputum to cause the slow formation of the phosphor precursor. The spray pyrolysis method is the aerosol method. - it is characterized by spraying a solution, suspension or knife spray onto a reaction space (reactor) heated in various ways by the meat η π type and solid particles are formed and deposited. And using a spray of hot air temperature Compared with drying, in the spray pyrolysis method which is g, w, ... as a method of retanning, in addition to the solvent, thermal decomposition of the starting material (for example, salt) used (for example, emulsion, mixed oxidation) Re-formation of matter).
上文已提及之6種方法變體詳細 购_27133·5(μ 這於 DE 申請案之上下文中。 ^心王文引用方式併入本 本發明之磷光體可藉由多種濕式化學方法如下製備： υ使組分均勻沈搬，接著將溶劑分離出，繼而進行單 驟或多步驟埶後虚琿 甘 , … 哪…傻處理，其中該等步驟之-可在還原性 氣氣下進行； 2)例如’藉助於喷霧方法將混合物精細分開，且移除容 劑，繼而進行單步驟或多步驟熱後處理，其中 驟之一可在還原性氣氛下進行；或 Λ , W ^如’藉助於噴霧方法將混合物精細分開’且結合熱 移除溶劑，繼而進行單步驟或多步驟熱後處理，其 中該等步驟之-可在還原性氣氛下進行； 、 4) t塗覆藉助於方法所製備之碌光體以使得折射率 適應其環境。 午 填光體之濕式化學製備較佳地藉由沈殺及/或溶膠-凝膠 129154.doc 200902685 方法進行。 :上文已提及之熱後處理中，較佳至少部分地在 件（例如使用一氧化碳、人 . ” , σ成虱體（formmg gas)、純氫或至 v真二或缺氧氣氛）下進行煅燒。 一般而言’亦可藉由固態擴散方法製備本發明之磷光 體，但該方法導致已提及之缺點。The six method variants mentioned above are detailed in _27133·5 (μ This is in the context of the DE application. ^Incorporating the phosphors of the present invention by reference to the invention can be carried out by various wet chemical methods as follows Preparation: υ to uniformly disperse the components, and then separate the solvent, followed by a single or multiple steps, then vain, ... which is silly, wherein the steps can be carried out under reducing gas; 2) For example, 'finely separate the mixture by means of a spray method, and remove the bulking agent, followed by a one-step or multi-step thermal after-treatment, wherein one of the steps can be carried out under a reducing atmosphere; or Λ, W ^如' The mixture is finely separated by means of a spraying method and the solvent is removed in combination with heat, followed by a one-step or multi-step thermal post-treatment, wherein the steps can be carried out under a reducing atmosphere; 4) t coating by means of a method The phosphor is prepared to adapt the refractive index to its environment. The wet chemical preparation of the noon fill is preferably carried out by the method of immersion and/or sol-gel 129154.doc 200902685. : the thermal aftertreatment already mentioned above, preferably at least partially under the component (for example using carbon monoxide, human.), σformmg gas, pure hydrogen or to v-true or anoxic atmosphere) Calcination is carried out. In general, the phosphor of the present invention can also be prepared by a solid state diffusion method, but this method leads to the disadvantages already mentioned.
上文已提及之方法致能待產生之4光體顆粒具有任何所 要外形，諸如球狀《、薄U結構化材料及陶竟。 作為另-較佳實施例，薄片形式填光體係藉由習知方法 由相應金屬及/或稀土金屬鹽製備。製備m細描述於 EP763573及抓咖㈣湘以中，該等專利以全文引用 方式併入本申請案之上下文中。該等薄片形式磷光體可如 下製備：藉由在水性分散液或懸浮液巾之賴反應，在具 極大縱枳比、原子平滑表面及可調節厚度的天然或合成 產生之高度穩定的（例如）雲母薄片、Si〇2薄片、Ai2〇3薄 片Zr〇2薄片、玻璃薄片或Ti〇2薄片之支撐物或基板上塗 覆璘光體層。除雲母' Zr〇2、Si〇2、从〇3、玻璃或Ti〇2或 八混合物以外，該等薄片亦可由磷光體材料自身組成或 由材料積聚而成。若薄片自身僅用作磷光體塗層之支撐 物，則後者必須由來自LED之初輻射可透過的材料組成， 或由吸收初輻射且將此能量傳遞至磷光體層之材料組成。 將薄片形式磷光體分散於樹脂（例如聚矽氧或環氧樹脂） 中，且將此分散液塗佈於led晶片上。該等薄片形式磷光 體可以50 nm至約20 μηι、較佳介於150 nm與5 μηι之間之厚 129l54.doc -16- 200902685 度以大工業規模製備。本文中之直徑為50 nm至20 μηι。其 一般具有1:1至400:1且尤其3:1至1〇〇:1之縱橫比（直徑與顆 粒厚度之比率）。薄片尺寸（長度χ寬度）視配置而定。薄片 亦適用作轉換層中之散射，尤其當其具有特別小之尺 寸時。本發明 <薄片$式磷光體朝向LED晶片之表面可具 備塗層’該塗層就LED晶片所發射之初輻射而言具有歧 射作用。此導致初ϋ射之背向散射減少，從而使後者在本 發明之磷光體元件中的耦接增強。The method already mentioned above enables the 4-light body particles to be produced to have any desired shape, such as a spherical shape, a thin U-structured material, and a ceramic. As a further preferred embodiment, the flake-form fill system is prepared from the corresponding metal and/or rare earth metal salt by conventional methods. The preparations are described in detail in EP 763 573 and in the context of the disclosure of the present application. The flake-form phosphors can be prepared by reacting in an aqueous dispersion or suspension to a highly stable (for example) natural or synthetically produced with a large aspect ratio, atomically smooth surface and adjustable thickness. A phosphor layer is coated on a support or substrate of mica flakes, Si〇2 flakes, Ai2〇3 flakes Zr〇2 flakes, glass flakes or Ti〇2 flakes. In addition to mica 'Zr〇2, Si〇2, from 〇3, glass or Ti〇2 or 八 mixtures, the sheets may also consist of or consist of a phosphor material. If the sheet itself is used only as a support for the phosphor coating, the latter must consist of a material that is permeable to radiation from the beginning of the LED, or a material that absorbs the initial radiation and transfers this energy to the phosphor layer. The thin-film form phosphor is dispersed in a resin such as polyfluorene oxide or epoxy resin, and this dispersion is applied onto a LED wafer. The flake-form phosphors can be prepared on a large industrial scale from 50 nm to about 20 μm, preferably between 150 nm and 5 μηι thick 129l54.doc -16-200902685 degrees. The diameter in this paper is 50 nm to 20 μηι. It typically has an aspect ratio (ratio of diameter to particle thickness) of 1:1 to 400:1 and especially 3:1 to 1〇〇:1. The sheet size (length χ width) depends on the configuration. The flakes are also suitable for scattering in the conversion layer, especially when they have a particularly small size. The present invention <flake $ phosphor can have a coating toward the surface of the LED wafer. The coating has an effect on the initial radiation emitted by the LED wafer. This results in a reduction in backscattering of the first shot, thereby enhancing the coupling of the latter in the phosphor element of the present invention.
適用於達成此目的者為（例如）折射率經調適之塗層，其 必須具有以下厚度d: d=[來自LED晶片之純射之波長/(4* 磷光體陶瓷之折射率）]，參見例如Gerthsen, Physik [Physics]，Springer VeHag，第 18版，1995。該塗層亦可由 光子晶體組成’其亦涵蓋使薄片形式麟光體之表面結構化 以實現某些功能。 製備陶竟元件形式之本發明碌光體係類似於DE 1020_3773G(Meixk)巾所述之方法來進行料利以全 文：用方式併入本申請案之上下文令。本文中之磷光體如 下製備.藉由濕式化學方法將相應起始材料及摻雜劑混 合，隨後均衡m合物且將混合物以均句、薄且無孔之 薄片形式直接塗佈至晶片表面H鱗光體之激勵及發 射並未發生位置依賴性變化’使得隨其所提供之LED發射 具有極定顏色的均勻弁名佳B目亡古2P _ 』尤錐且具有鬲發光功率。例如，陶瓷 麟：體元件可以數百奈米至約〜厚度之薄片形式以大 工：、規模產生。薄片尺寸（長度x寬度）視配置而定。在直 129154.doc 200902685 接塗佈於晶片上之情況下，薄片尺寸應根據晶片尺寸（約 1〇〇 μηι*100 μηι至若干⑺爪2)加以選擇，在合適晶片配置㈠列 如覆晶配置）或相應的情況下，晶片表面具有約10%-30% 之特定過量尺寸。若將磷光體薄片安裝在成品LED之頂 部’則所發射之光錐皆射中薄片。 陶瓷蝌光體元件之側表面可用輕金屬或貴金屬（較佳鋁 或銀）金屬化。金屬化具有使光無法自磷光體元件側向射 出之效應。側向射出之光可減少自LED中耦離出之光通 量。陶瓷磷光體元件之金屬化在均衡壓縮以得到桿或薄片 之後的方法步驟中進行，其中必要時可在金屬化之前以所 需尺寸切割桿或薄片。為達成此目的，例如用硝酸銀及葡 萄糖之溶液濕潤側表面，且隨後使其在高溫下曝露於氨氣 氛。在此操作期間’在側表面上形成（例如）銀塗層。或 者’無電極金屬化方法亦適合，參見例如H〇Uemann_ Wiberg, Lehrbuch der anorganischen Chemie [Textbook ofSuitable for achieving this is, for example, a refractive index-adapted coating which must have the following thickness d: d = [wavelength from pure shot of LED wafer / (4* refractive index of phosphor ceramic)], see For example, Gerthsen, Physik [Physics], Springer VeHag, 18th edition, 1995. The coating may also consist of a photonic crystal' which also encompasses structuring the surface of the sheet-form lining to achieve certain functions. The glazing system of the present invention in the form of a ceramic component is similar to the method described in DE 1020_3773G (Meixk), which is incorporated herein by reference in its entirety. The phosphors herein are prepared as follows. The corresponding starting materials and dopants are mixed by wet chemical methods, followed by equalizing the m compound and coating the mixture directly onto the wafer surface in a uniform, thin and non-porous sheet. The excitation and emission of the H scale body does not change position-dependently, so that the LED emission provided by the LED scale has a uniform color and a uniform color, and has a 鬲 luminous power. For example, ceramic lining: body components can be produced in large quantities: in the form of sheets of several hundred nanometers to about ~ thickness. The sheet size (length x width) depends on the configuration. In the case of straight 129154.doc 200902685 applied to the wafer, the sheet size should be selected according to the wafer size (about 1〇〇μηι*100 μηι to several (7) claws 2), in a suitable wafer configuration (a) column such as flip chip configuration Or, where appropriate, the wafer surface has a specific excess size of between about 10% and 30%. If the phosphor sheet is mounted at the top of the finished LED, the emitted light cones are incident on the sheet. The side surface of the ceramic phosphor element can be metallized with a light metal or a precious metal, preferably aluminum or silver. Metallization has the effect of preventing light from exiting laterally from the phosphor element. The laterally emitted light reduces the amount of light that is coupled out of the LED. The metallization of the ceramic phosphor elements is carried out in a method step after equalization of the compression to obtain a rod or sheet, wherein the rod or sheet can be cut in the desired size before metallization if necessary. To achieve this, the side surface is wetted, for example, with a solution of silver nitrate and glucose, and then exposed to an ammonia atmosphere at a high temperature. During this operation, for example, a silver coating is formed on the side surface. Or 'electrodeless metallization methods are also suitable, see for example H〇Uemann_ Wiberg, Lehrbuch der anorganischen Chemie [Textbook of
Inorganic Chemistry]，Waher de Gruyter Verlag，或 UllmannsInorganic Chemistry], Waher de Gruyter Verlag, or Ullmanns
Enzyklopadie der chemischen Technologie [Ullmann's Encyclopaedia of Chemical Technology]。有需要時，可使 用水玻璃溶液將陶瓷磷光體元件固定於LED晶片之基板 上。 在另一實施例中，陶瓷磷光體元件在led晶片之對面具 有結構化（例如錐狀）表面。此致能儘可能多之光耦離磷光 體元件。磷光體元件之結構化表面如下產生：使用具有結 構化壓板的模進行均衡壓縮且因此將結構壓印至表面内。 129154.doc -18- 200902685 若目標為產生可能最薄之磷光體元件或薄片，則需要結構 化表面。壓縮條件已為熟習此項技術者所知（參見j. Kriegsmann, Technische keramische Werkstoffe [Industrial 〜⑽卜，第4章，Deutscher驗⑽咖心㈣， 1998)。重要的是，所用之壓縮溫度為待壓縮物質之熔點 之 2/3 至 5/6。 此外，本發明之磷光體可在自約410 nm延伸至530 nm、 較佳自430 nm延伸至約5〇〇 nmi寬範圍内激發。因此，該 等磷光體不僅適用於藉*uv或發射藍光之初始光源（諸如 LED)或習知放電燈（例如，基於Hg)激發，且適用於光源， 例如利用451 nm處之藍光“3—譜線的彼等光源。 此外本發明亦係關於具有至少一初始光源之照明裝 置，該初始光源之最大發射在41〇 nm至530 nm範圍内，較 佳在430 nm至約500 nm範圍内，尤其較佳在44〇 11111至48〇 nmfe圍内，其中初輻射藉由本發明之磷光體部分地或完全 轉換為更長波長之輪射。該照明裝置較佳發射白光或發射 具有特定色點之光（按需取色原則）。本發明之照明裝置之 較佳實施例描繪於圖3-14中。 在本發明之照明裝置之一較佳實施例中，光源為發光性 氮化銦銘鎵，尤其具有式IniGajAlkN之氮化銦鋁鎵，其 中〇 < 1 ’ 〇 s j，〇 s k，且i十j + k=i。此類型光源之可能 形式已為熟習此項技術者所知。其可為具有各種結構之發 光LED晶片。 在本發明之照明裝置之另一較佳實施例中，光源為基於 129154.doc •19- 200902685Enzyklopadie der chemischen Technologie [Ullmann's Encyclopaedia of Chemical Technology]. If desired, the ceramic phosphor component can be attached to the substrate of the LED wafer with a water glass solution. In another embodiment, the ceramic phosphor component has a structured (e.g., tapered) surface on the face of the led wafer. This allows as much optocoupler as possible to be separated from the phosphor components. The structured surface of the phosphor element is created by equalizing compression using a mold having a structured platen and thus embossing the structure into the surface. 129154.doc -18- 200902685 A structured surface is required if the goal is to produce the thinnest possible phosphor element or sheet. Compression conditions are known to those skilled in the art (see j. Kriegsmann, Technische keramische Werkstoffe [Industrial ~ (10), Chapter 4, Deutscher (10) Ca Xin (4), 1998). It is important that the compression temperature used is from 2/3 to 5/6 of the melting point of the substance to be compressed. Furthermore, the phosphors of the present invention can be excited over a range extending from about 410 nm to 530 nm, preferably from 430 nm to about 5 〇〇 nmi. Therefore, the phosphors are not only suitable for use with an initial light source (such as an LED) that emits light or a blue light, or a conventional discharge lamp (for example, based on Hg), and are suitable for use in a light source, for example, using a blue light at 451 nm "3 - The present invention is also directed to an illumination device having at least one initial source having a maximum emission in the range of 41 〇 nm to 530 nm, preferably in the range of 430 nm to about 500 nm, It is particularly preferably within the range of 44〇11111 to 48〇nmfe, wherein the primary radiation is partially or completely converted to a longer wavelength by the phosphor of the present invention. The illumination device preferably emits white light or emits a specific color point. Light (on-demand color picking principle). A preferred embodiment of the illumination device of the present invention is depicted in Figures 3-14. In a preferred embodiment of the illumination device of the present invention, the light source is luminescent indium nitride In particular, indium aluminum gallium nitride having the formula IniGajAlkN, wherein 〇 < 1 ' 〇sj, 〇 sk, and i dec j + k = i. Possible forms of this type of light source are known to those skilled in the art. Can be a luminous L with various structures ED wafer. In another preferred embodiment of the illumination device of the present invention, the light source is based on 129154.doc • 19- 200902685
ZnO、TCO(透明導電氧化物）、ZnS^siC之發光配置或 基於有機發光層（OLED)之配置。 在本發明之照明裝置之另一較佳實施例中，光源為呈現 電致發光及/或光致發光之光源。此外，光源亦可為電漿 源或放電源。 本發明之磷光體可分散於樹脂（例如環氧樹脂或聚矽氧 樹脂）中，或在給定合適尺寸比之情況下可直接配置於初 始光源上，或視應用而定可與其遠距配置（後—配置亦包 括''遠距式磷光體技術”）。遠距式磷光體技術之優點已為熟 習此項技術者所知且揭示於（例如）以下公開案中： Japanese J〇urn· of Appl. phys，第 44卷，第 21期（2〇〇5)。 L649-L651 。 在另一實施例中，介於磷光體與初始光源之間之照明裝 置之光學耦合較佳地藉助於光導配置來實現。此致能初始 光源安裝在中央位置且藉助於光導設備（諸如光導纖維）與 磷光體光學耦聯。以此方式，可獲得與照明意願相匹配且 僅由一磷光體或不同磷光體（其可經配置以形成遮光板）與 光導體（其與初始光源耦聯）組成之燈。以此方式可將強 初始光源安置在有利於電學安裝之位置處且可將包含與光 導體耦聯之磷光體的燈安裝在任何所要位置處而無需其他 電缆架设’相反僅鋪設光導體即可。 此外，本發明亦係關於本發明之磷光體用於部分或完全 轉換發光二極體之藍光或近UV光發射之用途。 此外，本發明之磷光體較佳用於將藍光或近光發射 129154.doc •20· 200902685 轉換成可見白光輻射。此外，根據”按需取色”概念，本發 明之磷光體較佳用於將初輻射轉換成特定色點。 此外’本發明亦係關於本發明之磷光體在電致發光材料 (諸如電致發光膜（亦稱為發光膜或光膜））中之用途，其中 將（例如）硫化鋅或Mn2+、Cu+或Ag+摻雜之硫化鋅用作發射 極’其在黃光-綠光區中發射。電致發光膜之應用領域 為：例如’廣告；液晶顯示器螢幕（LC顯示器）及薄膜電晶 體（TFT)顯示器中之背光顯示；自發光性車輛牌照；地面 才示識（與抗壓及防滑層製品組合）；顯示及/或控制元件中 (例如，在汽車、火車、船隻及飛機，或以及家用電器、 庭園設備、量測儀器或運動及休閒設備中）。 【實施方式】 以下參考多個工作實例更詳細地解釋本發明。 以下實例旨在說明本發明。然而，決不應認為其具有限 制性。可用於該等組合物中之所有化合物或組分為已知的 且了市購’或可藉由已知方法合成。實例中所指示之溫度 始終以。C給出。此外，不言而喻，在說明以及實例中，組 合物中所添加之組分的量始終總計達1 〇〇%。所給之百分 比數據始終應視為具有給定聯繫。然而，其通常始終關於 所指示之部分量或總量之重量。 實例 實例1 :藉由滿式化學方法製備嗔光艘(υ〇93Α❶6Th_)3Als〇i2 將537.6 g碳酸氫銨溶解於3公升去離子水中。將2〇5 216 g氣化鋁六水合物' 151 522 g氣化釔六水合物、3 6i7吕氣 129154.doc •21 · 200902685 化鈽六水合物及0.1 91 g氣化灶（IV)溶解於約400 ml去離子 水中且快速地逐滴添加至碳酸氫鹽溶液中。在此添加期 間’必須藉由添加濃氨水使pH值保持在pH 8。隨後，將該 混合物再攪拌一小時。老化後’將沈澱物濾出且在乾燥箱 中在約120°C下乾燥。 將經乾燥之沈激物在研妹中研磨且隨後在空氣中在 1000°C下煅燒4小時。隨後，將產物在研缽中再研磨且在 氫氣/氬氣氛下在1700°C下煅燒8小時。 實例2 :藉由濕式化學方法製備磷光體(Ye 939Ce<u)6BiQeGi)3Al5〇i2 將537.6 g碳酸氫銨溶解於3公升去離子水中。將2〇5216 g 氣化鋁六水合物、151.522 g氣化釔六水合物、3 617 g氣化 鈽六水合物及0.161 g氣化鉍（ΠΙ)溶解於約4〇〇 ml去離子水 中且快速地逐滴添加至碳酸氫鹽溶液中。在此添加期間， 必須藉由添加濃氨水使pH值保持在pH 8。隨後，將該混合 物再授拌一小時。老化後，將沈澱物濾出且在乾燥箱中在 約120°C下乾燥。 將經乾燥之沈澱物在研缽中研磨且隨後在空氣中在 1000°C下煅燒4小時。隨後，將產物在研蛛中再研磨且在 氫氣/氬氣氛下在17 〇 0 °C下般燒8小時。 實例3 :藉由漁式化學方法製備_光艘(Y〇 939Ce"6Sb"〇i)3Al5〇i2 將537.6 反虱知溶解於3公升去離子水中。將205.216 g氯化鋁六水合物、151.522 g氣化釔六水合物、3 617 g氯 化鈽六水合物及0.116 g氣化銻（111)溶解於約4〇〇 ml去離子 水中且快速地逐滴添加至碳酸氫鹽溶液中b在此添加期 129154.doc -22- 200902685 間，必須藉由添加濃氨水使1311值保持在pH 8。隨後，將該 混合物再攪拌一小時。老化後’將沈澱物濾出且在乾燥箱 中在約120°C下乾燥。 將經乾燥之沈澱物在研缽中研磨且隨後在空氣中在 1000 C下煅燒4小時。隨後’將產物在研缽中再研磨且在 氫氣/氬氣氛下在17〇〇。(：下煅燒8小時。 實例4 :藉由混合及燒製方法（固態擴散）製備YAG:Ce(Ce 接雜濃度 2%，Y2.94Als012:CeG,()63+) 稱取0.344 g二氧化鈽（Ce〇2)、33 646 g氧化釔（γ2〇3)及 25.491 g氧化鋁（八丨2〇3)且用水製成漿料。使用少量水，在 研蛛中濕式研磨該混合物。接著，將漿料轉移至箱型爐 中，在箱型爐中經6 h時期在合成氣體氣氛下在12〇〇它溫度 下對其進行煅燒。冷卻後，再次將該材料精細研磨且經8 小時時期使其在爐中在17〇(rc溫度下經受還原性煅燒。 實例5:藉由濕式化學方法製備YAG:Ce(Ce摻雜濃度為 2%，Y2.94Al5O12:Ce0.063+) 將537.6 g碳酸氫銨溶解於3公升去離子水中。將2〇52i6 g氯化鋁六水合物、153.242 g氯化釔六水合物及3 617 §氣 化鈽六水合物溶解於約400 ml去離子水中且快速地逐滴添 加至碳酸氫鹽溶液中。在此添加期間，必須藉由添加濃氨 水使pH值保持在pH 8。隨後，將該混合物再攪拌一小時。 老化後，將沈澱物濾出且在乾燥箱中在約12〇。〇下乾燥。 將經乾燥之沈殿物在研钵中研磨且隨後在空氣中在 1000°C下煅燒4小時。隨後，將產物在研缽中再研磨且在 129154.doc •23· 200902685 氫氣/氬氣氛下在1700°C下煅燒8小時。 實例6至8:藉由混合及燒製方法（固態擴散）製備碟光鱧 (Y〇.98-xCe〇.〇2Thx)3Al5〇12 * 其中 Χ = 〇·〇〇1， χ=0·0025及 χ=0·005 稱出12.5 mmol之γ-氧化銘A12〇3、7.35 mmol-χ之氧化在乙 Y2O3、0.3 mmol 二氧化飾 Ce〇2 及 0.015 mmol < X < 〇 075 mmol之氧化钍Th〇2。隨後，用丙酮將起始材料製成聚料 且於研缽中充分研磨。在第一煅燒步驟中，將樣品在一氧 5 化碳下在1200°C下加熱兩小時。在研妹中進一步充分研磨 之後，進行第二煅燒步驟，其中同樣在一氧化碳氣氛下在 16 5 0 °C下將該批料加熱四小時。 在研缽中進行最終研磨之後’藉由X射線粉末繞射、螢 光光譜學及反射光譜學表徵樣品。 【圖式簡單說明】 圖1 :與藉由固態擴散反應（混合及燒製）所製備之含有 2% Ce的市購純YsAlsOaCe及藉由濕式化學方法所製備之 * 純YAG:Ce(前驅物）相比，本發明之磷光體（Y，Bi)3Ai5〇u Ce、 (Y，Th)3Al5012:Ce及（Y，Sb)3Al5〇12:ce之發射光譜。激發波長 為 450 nm(X 軸：LAMBDA/nm=波長/nm ; y軸：Ιιη_ —= 螢光強度/任意單位）。 圖2a .發射光谱之放大圖以較佳地說明不同的最大發 射。藉由濕式化學方法所製備且經Bi、几或別摻雜之本發 明磷光體驚人地具有比藉由固態擴散反應所製備之市講純 YAG:Ce及藉由濕式化學方法所製備的純YAG:Ce更高之螢 129154.doc -24 - 200902685 光強度。 (x，y)CIE 1937色度圖中之色點： (Y〇.969Ce0.〇2X〇.〇〇i)3Al5〇12， 其中 X=Sb : (x/y)=0.438/0.541 ; 其中 X=Bi : (x/y) = 〇.440/0.539 ; 其中 X=Th : (x/y)=〇.439/0.541。 藉由固態擴散反應製備之市購YAG:Ce : (x/y)=0.435/0.541。 藉由濕式化學方法所製備之YAG:Ce : (x/y)=0.435/0.541。 圏 2b:本發明之磷光體（Y，Bi)3A15〇i2:Ce& (Y，Th)3Al5〇i2:Ce 之發射光譜，與非共摻雜YAG:Ce相比，其已藉由固態擴 散反應（混合及燒製）製備。 圖3:展示具有含磷光體塗層之發光二極體之圖示。該 組件包含晶片樣發光二極體（LED)1作為輻射源。該發光二 極體係女裝於藉由調節框架所固持之杯形反射器2中。晶 片1經由扁電纜7連接至第一接點6且直接連接至第二電接 點6，。包含本發明之轉換磷光體的塗層已經塗佈於反射杯 之内部曲面。鱗光體彼此單獨使用或作為混合物使用。 (牛編唬清單：1發光二極體；2反射器；3樹脂；4轉換 璘光體；5擴散體；6電極；7扁電纜）。 圓4 :展示InGaN型之C0B(板上晶片）封裝，其充當白光 之光源（LED)( 1 =半導體晶片；2、3=電連接；4 =轉換磷光 體；7 =板）。將磷光體分布於黏結劑透鏡中，其同時代表 129154.doc -25- 200902685 第二光學元件且作為透鏡影響光發射特性。 圖5 :展示InGaN型之COB(板上晶片）封裝，其充當白光 之光源（LED)( 1 =半導體晶片；2、3=電連接；4=轉換麟光 體；7 =板）。磷光體位於、分布於直接位於lEd晶片上之 黏結劑薄層中。由透明材料組成之第二光學元件可置放於 其上。 圖6 :展示充當白光之光源（led)的Golden Drag〇n®封裝 (1-半導體晶片，2、3-電連接；4 =具有反射器之空腔内的 轉換磷光體）。轉換磷光體分散於黏結劑中，其中混合物 填充該空腔。 外殼；2=電連接；3 =透 圖7 :展示Luxeon®封裝，其中1 鏡；4=半導體晶片。該設計具有覆晶設計之優點，其中經A luminescent arrangement of ZnO, TCO (transparent conductive oxide), ZnS^siC or an organic light-emitting layer (OLED) based configuration. In another preferred embodiment of the illumination device of the present invention, the light source is a light source that exhibits electroluminescence and/or photoluminescence. In addition, the light source can also be a plasma source or a discharge source. The phosphor of the present invention may be dispersed in a resin such as an epoxy resin or a polyoxynoxy resin, or may be directly disposed on an initial light source at a given size ratio, or may be remotely disposed depending on the application. (After-configuration also includes ''distant phosphor technology'). The advantages of remote phosphor technology are known to those skilled in the art and are disclosed, for example, in the following publication: Japanese J〇urn· Of Appl. phys, Vol. 44, No. 21 (2〇〇5). L649-L651. In another embodiment, the optical coupling of the illumination device between the phosphor and the initial source is preferably by means of The light guide arrangement is implemented. This enables the initial light source to be mounted in a central position and optically coupled to the phosphor by means of a light guiding device, such as an optical fiber. In this way, it is possible to match the willingness to illuminate and consist of only one phosphor or different phosphorescence. a body (which may be configured to form a visor) and a light conductor (which is coupled to the initial source). In this manner, a strong initial light source can be placed at a location that facilitates electrical installation and can include and light guides The body-coupled phosphor lamp is mounted at any desired location without the need for additional cable erections. Instead, only the photoconductor is laid. In addition, the present invention also relates to the phosphor of the present invention for partially or fully converting the light-emitting diode. In addition, the phosphor of the present invention is preferably used to convert blue or low-beam emission 129154.doc • 20· 200902685 into visible white light radiation. In addition, according to "on-demand color picking" Concepts, the phosphor of the present invention is preferably used to convert primary radiation to a particular color point. Furthermore, the present invention is also directed to phosphors of the present invention in electroluminescent materials such as electroluminescent films (also known as luminescent films or Use in a light film)) in which, for example, zinc sulfide or Mn2+, Cu+ or Ag+ doped zinc sulfide is used as an emitter, which emits in a yellow-green region. The field of application of the electroluminescent film is : for example, 'advertising; backlight display in liquid crystal display screen (LC display) and thin film transistor (TFT) display; self-illuminating vehicle license plate; ground recognition (combined with anti-pressure and anti-slip layer products); And/or control elements (for example, in automobiles, trains, boats and airplanes, or in household appliances, garden equipment, measuring instruments, or sports and leisure equipment). [Embodiment] The following is a more detailed description with reference to a plurality of working examples. The invention is illustrated by the following examples. However, it should not be considered as limiting. All compounds or components useful in such compositions are known and commercially available or may have been The method is known to synthesize. The temperature indicated in the examples is always given by C. Furthermore, it goes without saying that in the description and the examples, the amount of components added in the composition always amounts to 1%. The percentage data should always be considered to have a given relationship. However, it is usually always about the weight of the indicated portion or total amount. EXAMPLES Example 1: Preparation of Twilight Ship (υ〇93Α❶6Th_)3Als〇i2 by Full Chemical Method 537.6 g of ammonium hydrogencarbonate was dissolved in 3 liters of deionized water. Dissolve 2〇5 216 g of vaporized aluminum hexahydrate '151 522 g gasified hydrazine hexahydrate, 3 6i7 lyophile 129154.doc •21 · 200902685 hydrazine hexahydrate and 0.1 91 g gasification stove (IV) It was added to the bicarbonate solution in about 400 ml of deionized water and rapidly added dropwise. During this addition, the pH must be maintained at pH 8 by the addition of concentrated aqueous ammonia. Subsequently, the mixture was stirred for another hour. After aging, the precipitate was filtered off and dried at about 120 ° C in a dry box. The dried sink was ground in a graduated room and then calcined in air at 1000 ° C for 4 hours. Subsequently, the product was reground in a mortar and calcined at 1,700 ° C for 8 hours under a hydrogen/argon atmosphere. Example 2: Preparation of Phosphor by Wet Chemical Method (Ye 939Ce<u)6BiQeGi)3Al5〇i2 537.6 g of ammonium hydrogencarbonate was dissolved in 3 liters of deionized water. 2〇5216 g of vaporized aluminum hexahydrate, 151.522 g of gasified hydrazine hexahydrate, 3 617 g of gasified hydrazine hexahydrate and 0.161 g of gasified hydrazine (ΠΙ) were dissolved in about 4 〇〇ml of deionized water and It is quickly added dropwise to the bicarbonate solution. During this addition, the pH must be maintained at pH 8 by the addition of concentrated aqueous ammonia. Subsequently, the mixture was further mixed for one hour. After aging, the precipitate was filtered off and dried in a dry box at about 120 °C. The dried precipitate was ground in a mortar and then calcined in air at 1000 ° C for 4 hours. Subsequently, the product was reground in a spider and fired under a hydrogen/argon atmosphere at 17 ° C for 8 hours. Example 3: Preparation by Fishery Chemical Method _Guangzhou (Y〇 939Ce"6Sb"〇i)3Al5〇i2 Dissolve 537.6 in 3 liters of deionized water. Dissolving 205.216 g of aluminum chloride hexahydrate, 151.522 g of gasified ruthenium hexahydrate, 3 617 g of ruthenium chloride hexahydrate and 0.116 g of ruthenium osmium (111) in about 4 〇〇ml of deionized water and rapidly Adding dropwise to the bicarbonate solution b During this addition period 129154.doc -22- 200902685, the 1311 value must be maintained at pH 8 by the addition of concentrated aqueous ammonia. Subsequently, the mixture was stirred for another hour. After aging, the precipitate was filtered off and dried at about 120 ° C in a dry box. The dried precipitate was ground in a mortar and then calcined in air at 1000 C for 4 hours. The product was then reground in a mortar and at 17 Torr under a hydrogen/argon atmosphere. (: calcination for 8 hours. Example 4: Preparation of YAG by mixing and firing method (solid diffusion): Ce (Ce concentration 2%, Y2.94Als012: CeG, () 63+) Weigh 0.344 g of dioxide钸 (Ce 〇 2), 33 646 g yttrium oxide (γ 2 〇 3) and 25.491 g alumina (bar 丨 2 〇 3) and slurried with water. The mixture was wet-milled in a spider using a small amount of water. Next, the slurry was transferred to a box furnace, which was calcined in a box furnace at a temperature of 12 Torr under a synthesis gas atmosphere for 6 h. After cooling, the material was again finely ground and passed through 8 It was subjected to reductive calcination in an oven at 17 Torr (hour temperature). Example 5: Preparation of YAG by a wet chemical method: Ce (Ce doping concentration: 2%, Y2.94Al5O12: Ce0.063+) Dissolve 537.6 g of ammonium bicarbonate in 3 liters of deionized water. Dissolve 2〇52i6 g of aluminum chloride hexahydrate, 153.242 g of ruthenium chloride hexahydrate and 3 617 § gasified ruthenium hexahydrate in about 400 ml. Ionized water and quickly added dropwise to the bicarbonate solution. During this addition, the pH must be maintained at pH 8 by the addition of concentrated aqueous ammonia. The mixture was stirred for an additional hour. After aging, the precipitate was filtered off and dried in a dry box at about 12 Torr. The dried slab was ground in a mortar and then at 1000 ° C in air. Calcination for 4 hours. Subsequently, the product was reground in a mortar and calcined at 1700 ° C for 8 hours under a hydrogen/argon atmosphere at 129154.doc • 23· 200902685. Examples 6 to 8: by mixing and firing methods ( Solid state diffusion) Preparation of disc 鳢 (Y〇.98-xCe〇.〇2Thx)3Al5〇12 * where Χ = 〇·〇〇1, χ=0·0025 and χ=0·005 Weigh 12.5 mmol γ- Oxidation of A12〇3, 7.35 mmol-χ oxidation in E2O3, 0.3 mmol of oxidized CeC2 and 0.015 mmol < X < 〇075 mmol of yttrium oxide Th〇2. Subsequently, starting materials with acetone The pellet was prepared and thoroughly ground in a mortar. In the first calcination step, the sample was heated at 1200 ° C for two hours under an oxygenated carbon. After further grinding in the Yanmei, a second calcination was carried out. a step in which the batch is heated under a carbon monoxide atmosphere at 1650 ° C for four hours. Final grinding in a mortar The sample is characterized by X-ray powder diffraction, fluorescence spectroscopy and reflectance spectroscopy. [Simplified illustration] Figure 1: 2% Ce prepared by solid state diffusion reaction (mixing and firing) The commercially available pure YsAlsOaCe and the pure YAG:Ce (precursor) prepared by the wet chemical method, the phosphor (Y,Bi)3Ai5〇u Ce, (Y,Th)3Al5012:Ce and (Y, Sb) 3Al5〇12: ce emission spectrum. The excitation wavelength is 450 nm (X-axis: LAMBDA/nm = wavelength / nm; y-axis: Ιιη_ - = fluorescence intensity / arbitrary unit). Figure 2a. An enlarged view of the emission spectrum to better illustrate the different maximum emissions. Phosphors of the invention prepared by wet chemical methods and Bi, slightly or doped, surprisingly have a ratio of YAG:Ce prepared by solid state diffusion reaction and prepared by wet chemical methods. Pure YAG: Ce higher fire 129154.doc -24 - 200902685 light intensity. (x, y) CIE 1937 color point in the chromaticity diagram: (Y〇.969Ce0.〇2X〇.〇〇i)3Al5〇12, where X=Sb : (x/y)=0.438/0.541 ; where X =Bi : (x/y) = 〇.440/0.539 ; where X=Th : (x/y)=〇.439/0.541. Commercially available YAG prepared by solid state diffusion reaction: Ce: (x/y) = 0.435/0.541. YAG prepared by wet chemical method: Ce: (x/y) = 0.435/0.541.圏2b: The emission spectrum of the phosphor (Y,Bi)3A15〇i2:Ce&(Y,Th)3Al5〇i2:Ce of the present invention, which has been diffused by solid state compared with non-codoped YAG:Ce The reaction (mixing and firing) is prepared. Figure 3: shows an illustration of a light-emitting diode with a phosphor-containing coating. The assembly includes a wafer-like light emitting diode (LED) 1 as a source of radiation. The light-emitting diode system is housed in a cup-shaped reflector 2 held by an adjustment frame. The wafer 1 is connected to the first contact 6 via a flat cable 7 and directly connected to the second electrical contact 6. The coating comprising the conversion phosphor of the present invention has been applied to the inner curved surface of the reflector cup. The scales are used alone or as a mixture. (Cattle compilation list: 1 light-emitting diode; 2 reflector; 3 resin; 4 conversion phosphor; 5 diffuser; 6 electrode; 7 flat cable). Circle 4: Shows an InGaN type C0B (on-board wafer) package that acts as a white light source (LED) (1 = semiconductor wafer; 2, 3 = electrical connection; 4 = conversion phosphor; 7 = plate). The phosphor is distributed in the binder lens, which simultaneously represents the second optical component of 129154.doc -25-200902685 and affects the light emission characteristics as a lens. Figure 5: shows an InGaN type COB (on-board wafer) package that acts as a white light source (LED) (1 = semiconductor wafer; 2, 3 = electrical connection; 4 = conversion lining; 7 = plate). The phosphor is located in a thin layer of binder that is directly on the lEd wafer. A second optical element composed of a transparent material can be placed thereon. Figure 6: shows the Golden Drag〇n® package (1-semiconductor wafer, 2, 3-electrical connection; 4 = conversion phosphor in the cavity with reflector) acting as a white light source (led). The conversion phosphor is dispersed in the binder, wherein the mixture fills the cavity. Housing; 2 = electrical connection; 3 = through Figure 7: Show Luxeon® package with 1 mirror; 4 = semiconductor wafer. The design has the advantages of flip chip design, in which
的光用於照明目的。此外，該設計有利於熱散逸。 圖8 :展示一種封裝， 晶片’且透鏡下方之1 其中1 =外殼；2=電連接；4=半導The light is used for lighting purposes. In addition, the design facilitates heat dissipation. Figure 8: shows a package, wafer 'and 1 below the lens where 1 = outer casing; 2 = electrical connection; 4 = semi-conductive
可充當遠距式磷光體。Can act as a remote phosphor.
可裝配於習知燈中。Can be assembled in a conventional lamp.
129154.doc •26- 200902685 晶片之背面，其優點在於磷光體經由金屬連接加以冷卻。 圖11 ··展示發光二極體之圖示，其中1 =半導體晶片； 2.3 =電連接；4 =轉換磷光體；5 =接合線’其中磷光體在黏 、、’=劑中用作頂部球體。磷光體/黏結劑層之此形式可充當 第二光學元件且影響（例如）光傳播。 圖12 :展示發光二極體之圖示，其中1 =半導體晶片； 2.3 =電連接；4 =轉換磷光體；5 =接合線，其中磷光體在黏 結劑中應用、分散為薄層。充當第二光學元件之其他組件129154.doc •26- 200902685 The back side of the wafer has the advantage that the phosphor is cooled via a metal connection. Figure 11 · shows an illustration of a light-emitting diode, where 1 = semiconductor wafer; 2.3 = electrical connection; 4 = conversion phosphor; 5 = bonding wire 'where the phosphor is used as a top sphere in the adhesion, '= agent . This form of phosphor/adhesive layer can act as a second optical element and affect, for example, light propagation. Figure 12: shows an illustration of a light-emitting diode, where 1 = semiconductor wafer; 2.3 = electrical connection; 4 = conversion phosphor; 5 = bonding wire, wherein the phosphor is applied and dispersed as a thin layer in the binder. Acting as a component of the second optical component
(铕如逯鏡）可易於應用於此層上。 圓13 :展示原則上已根據US-B 6,700,322所知之其他應 用之實例。在本文中，本發明之磷光體連同〇LED 一起使 用。光源為由實際有機膜3〇及透明基板32組成之有機發光 二極體31。膜30尤其發射初始藍光，該膜（例如）藉助於 PVK:PBD :香豆素（PVK :聚（N-乙烯基咔唑）之縮寫； PBD : 2-(4-聯苯）_5_(4_第三丁基_苯基）惡二唾之縮 寫）而產生。藉由本發明之磷光體層33所形成的覆蓋層使 發射。P刀地轉換成黃色二次發射光，以致藉由將初始發射 光與二次發射光之顏色混合獲得總體白光發射。〇咖大 體上由至少一層發光聚合物或介於兩電極之間的所謂小八 子組成，肖等電極由作為陽極之本身已知 ： ιτο(乳化銦錫之縮寫））及作為陰極 口 DO·、 度反應性金屬（諸 如或叫組成。電極之間通常亦使用複數個層，★ :傳遞層^在小分子領域内亦充當電子傳遞層:、例：電 斤用之發光聚合物為聚苐或聚螺材料。 129I54.doc -27- 200902685 圖14 :展示與WO 2005/061659類似，具有無汞氣體填充 物2 1(含有銦填充物及緩衝氣體）之低壓燈（圖示），其中應 用本發明之磷光體層22。 【主要元件符號說明】 1 發光二極體/晶片 1 半導體晶片 1 外殼 2 反射器 2 電連接 2 晶片 2、3 電連接 3 透鏡 3 樹脂 4 半導體晶片 4 轉換磷光體 4 轉換層 5 擴散體 5 具有透明樹脂之透鏡 5 接合線 6 電極/第一接點 7 扁電纜 7 板 20 低壓燈 21 無汞氣體填充物 129154.doc -28- 200902685 22 磷光體層 30 實際有機膜 31 有機發光二極體 32 透明基板 33 磷光體層 129154.doc -29-(such as a frog mirror) can be easily applied to this layer. Circle 13: shows examples of other applications that are known in principle from US-B 6,700,322. Herein, the phosphor of the present invention is used together with a ruthenium LED. The light source is an organic light-emitting diode 31 composed of an actual organic film 3A and a transparent substrate 32. The film 30 in particular emits an initial blue light, for example by means of PVK: PBD: coumarin (PVK: poly(N-vinylcarbazole) abbreviation; PBD: 2-(4-biphenyl)_5_(4_ Produced by the third butyl-phenyl) abbreviation of dioxin. The cover layer formed by the phosphor layer 33 of the present invention emits light. The P blade is converted into a yellow secondary emission light so that the overall white light emission is obtained by mixing the initial emission light with the color of the secondary emission light. The coffee is generally composed of at least one layer of a light-emitting polymer or a so-called small eight between the two electrodes, and the electrode such as a mirror is known per se as an anode: ιτο (abbreviation of emulsified indium tin) and as a cathode port DO·, Degree-reactive metal (such as or composition). Usually a plurality of layers are also used between the electrodes, ★: the transfer layer ^ also acts as an electron transport layer in the small molecule field: for example: the light-emitting polymer used for the charge is polyfluorene or Polyspirate material. 129I54.doc -27- 200902685 Figure 14: shows a low-pressure lamp (shown) with mercury-free gas filling 21 (containing indium filler and buffer gas) similar to WO 2005/061659, in which the application Inventive phosphor layer 22. [Main element symbol description] 1 Light-emitting diode/wafer 1 Semiconductor wafer 1 Case 2 Reflector 2 Electrical connection 2 Wafer 2, 3 Electrical connection 3 Lens 3 Resin 4 Semiconductor wafer 4 Conversion phosphor 4 Conversion Layer 5 Diffusion body 5 Lens with transparent resin 5 Bonding wire 6 Electrode / First contact 7 Flat cable 7 Plate 20 Low voltage lamp 21 Mercury-free gas filling 129154.doc -28- 200902685 22 Phosphor layer 30 Actual organic film 31 Organic light-emitting diode 32 Transparent substrate 33 Phosphor layer 129154.doc -29-
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2007
- 2007-03-06 DE DE102007010719A patent/DE102007010719A1/en not_active Withdrawn
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2008
- 2008-02-13 KR KR1020097020806A patent/KR101487040B1/en not_active IP Right Cessation
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- 2008-02-13 CN CN200880007397XA patent/CN101641425B/en not_active Expired - Fee Related
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- 2008-03-06 TW TW097107946A patent/TWI462991B/en not_active IP Right Cessation
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| US9567519B2 (en) | 2012-03-29 | 2017-02-14 | Merck Patent Gmbh | Composite ceramic which comprises a conversion phosphor and a material having a negative coefficient of thermal expansion |
| TWI594969B (en) * | 2012-03-29 | 2017-08-11 | 馬克專利公司 | Composite ceramic |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2115092A1 (en) | 2009-11-11 |
| CN101641425B (en) | 2013-05-01 |
| JP5313173B2 (en) | 2013-10-09 |
| DE502008003422D1 (en) | 2011-06-16 |
| KR101487040B1 (en) | 2015-01-28 |
| US8088304B2 (en) | 2012-01-03 |
| US20100084962A1 (en) | 2010-04-08 |
| TWI462991B (en) | 2014-12-01 |
| EP2115092B1 (en) | 2011-05-04 |
| KR20100015388A (en) | 2010-02-12 |
| DE102007010719A1 (en) | 2008-09-11 |
| JP2010520337A (en) | 2010-06-10 |
| CN101641425A (en) | 2010-02-03 |
| WO2008107062A1 (en) | 2008-09-12 |
| ATE508178T1 (en) | 2011-05-15 |
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